JPH03237131A - End modified polyether amide resin - Google Patents
End modified polyether amide resinInfo
- Publication number
- JPH03237131A JPH03237131A JP3473390A JP3473390A JPH03237131A JP H03237131 A JPH03237131 A JP H03237131A JP 3473390 A JP3473390 A JP 3473390A JP 3473390 A JP3473390 A JP 3473390A JP H03237131 A JPH03237131 A JP H03237131A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- group
- groups
- terminal
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002614 Polyether block amide Polymers 0.000 title claims abstract description 33
- 229920005989 resin Polymers 0.000 title claims abstract description 26
- 239000011347 resin Substances 0.000 title claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 10
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 7
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 20
- 235000013305 food Nutrition 0.000 abstract description 7
- 238000000465 moulding Methods 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 238000004806 packaging method and process Methods 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 239000000470 constituent Substances 0.000 abstract 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract 1
- 239000004952 Polyamide Substances 0.000 description 23
- 229920002647 polyamide Polymers 0.000 description 23
- -1 Poly(ether amide Chemical class 0.000 description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 21
- 125000003277 amino group Chemical group 0.000 description 19
- 239000002253 acid Substances 0.000 description 17
- 229920000570 polyether Polymers 0.000 description 13
- 239000004721 Polyphenylene oxide Substances 0.000 description 12
- 150000004985 diamines Chemical class 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 5
- 150000003951 lactams Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 150000003384 small molecules Chemical class 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000011191 terminal modification Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- IWTMSCUHCJHPPR-ACCUITESSA-N (E)-hexadec-2-enedioic acid Chemical compound OC(=O)CCCCCCCCCCCC\C=C\C(O)=O IWTMSCUHCJHPPR-ACCUITESSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- JPZYXGPCHFZBHO-UHFFFAOYSA-N 1-aminopentadecane Chemical compound CCCCCCCCCCCCCCCN JPZYXGPCHFZBHO-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- REHQLKUNRPCYEW-UHFFFAOYSA-N 1-methylcyclohexane-1-carboxylic acid Chemical compound OC(=O)C1(C)CCCCC1 REHQLKUNRPCYEW-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- HASUJDLTAYUWCO-UHFFFAOYSA-N 2-aminoundecanoic acid Chemical compound CCCCCCCCCC(N)C(O)=O HASUJDLTAYUWCO-UHFFFAOYSA-N 0.000 description 1
- CGMMPMYKMDITEA-UHFFFAOYSA-N 2-ethylbenzoic acid Chemical compound CCC1=CC=CC=C1C(O)=O CGMMPMYKMDITEA-UHFFFAOYSA-N 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- VWPQCOZMXULHDM-UHFFFAOYSA-N 9-aminononanoic acid Chemical compound NCCCCCCCCC(O)=O VWPQCOZMXULHDM-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- JJOJFIHJIRWASH-UHFFFAOYSA-N Eicosanedioic acid Natural products OC(=O)CCCCCCCCCCCCCCCCCCC(O)=O JJOJFIHJIRWASH-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N Methylcyclohexane Natural products CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 description 1
- 229920001007 Nylon 4 Polymers 0.000 description 1
- SBLKVIQSIHEQOF-UPHRSURJSA-N Octadec-9-ene-1,18-dioic-acid Chemical compound OC(=O)CCCCCCC\C=C/CCCCCCCC(O)=O SBLKVIQSIHEQOF-UPHRSURJSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- CJYXCQLOZNIMFP-UHFFFAOYSA-N azocan-2-one Chemical compound O=C1CCCCCCN1 CJYXCQLOZNIMFP-UHFFFAOYSA-N 0.000 description 1
- YDLSUFFXJYEVHW-UHFFFAOYSA-N azonan-2-one Chemical compound O=C1CCCCCCCN1 YDLSUFFXJYEVHW-UHFFFAOYSA-N 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000007278 cyanoethylation reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KAJZYANLDWUIES-UHFFFAOYSA-N heptadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCN KAJZYANLDWUIES-UHFFFAOYSA-N 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- BUHXFUSLEBPCEB-UHFFFAOYSA-N icosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCN BUHXFUSLEBPCEB-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229940116918 octadecenedioic acid Drugs 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
Landscapes
- Polyamides (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、末端が変性されたポリエーテルアミド樹脂に
関する。詳しくは、本発明は易抽出低分子化合物を低減
化し、しかも成形後(熱履歴後)の低分子化合物発生の
少ない、熱安定性良好なポリエーテルアミド樹脂に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to terminally modified polyetheramide resins. Specifically, the present invention relates to a polyetheramide resin which has a reduced amount of easily extracted low molecular weight compounds, generates less low molecular weight compounds after molding (after heat history), and has good thermal stability.
ポリエーテルアミド樹脂は耐電防止性、耐熱性成形性、
機械的強度にすぐれ種々の用途に使用されるが(例えば
特公昭45−7559)、最近ではその柔軟性や機械的
強度から食品包装分野、特に食品包装用フィルムやシー
トでの使用が検討されている。Polyetheramide resin has antistatic properties, heat resistant moldability,
It has excellent mechanical strength and is used for various purposes (for example, Japanese Patent Publication No. 45-7559), but recently its use in the food packaging field, especially in food packaging films and sheets, has been considered due to its flexibility and mechanical strength. There is.
しかしながら、ポリエーテルアミド樹脂は、その溶融重
合時に低分子臭気物質やポリアミドオリゴマー等の低分
子化合物が生成するため、食品関連分野での使用が敬遠
されていた。しかも低分子化合物を適切な溶剤で一度除
去しても、溶融成形すると再度発生するので、熱安定性
の点でも好ましくなく、従って更なる改良が望まれてい
た。However, polyetheramide resins have been avoided in food-related fields because they produce low-molecular-weight odorous substances and low-molecular compounds such as polyamide oligomers during their melt polymerization. Moreover, even if the low-molecular-weight compound is once removed using an appropriate solvent, it will be generated again when melt-molding is performed, which is not desirable in terms of thermal stability.Therefore, further improvements have been desired.
本発明者らは上記問題を解決すべく鋭意研究を重た結果
、ポリエーテルアミド樹脂が必然的に保有するポリマー
分子末端であるア〔)基及びカルボキシ基が低分子臭気
物質及びその他の低分子化合物の発生に関与しているこ
とを見出した。そして、このアミノ基及びカルボキシ基
を特定の炭化水素基で封止することによって上記低分子
化合物等の発生が大巾に抑制される事を知得して本発明
を完成した。The present inventors have conducted intensive research to solve the above problem, and have found that the a[) group and the carboxy group at the end of the polymer molecule, which polyether amide resin inevitably has, can be used for low-molecular-weight odorous substances and other low-molecular-weight substances. It was found that this compound is involved in the generation of compounds. The present invention was completed based on the knowledge that by sealing these amino groups and carboxy groups with specific hydrocarbon groups, the generation of the above-mentioned low-molecular compounds, etc. can be greatly suppressed.
即ち、本発明は工業的価値の大きいポリエーテルアミド
樹脂を提供することを目的とするものであり、その要旨
とするところは
下記構造式(1〕、 ([〕、(1)又は〔IV〕で
示される構成単位からなり、末端に炭素数1〜22の炭
化水素基を有する分子量10,000〜10.000の
ポリエーテルアミドであり、該炭化水素基の数が該ポリ
エーテルアミドの全末端基の数の5〜100%である末
端変性ポリエーテルアミド樹脂。That is, the purpose of the present invention is to provide a polyetheramide resin having great industrial value, and the gist thereof is the following structural formula (1), ([], (1) or [IV] It is a polyether amide having a molecular weight of 10,000 to 10,000 and having a hydrocarbon group having 1 to 22 carbon atoms at the terminal, and the number of the hydrocarbon groups is equal to the total number of terminals of the polyether amide. A terminal-modified polyetheramide resin having 5 to 100% of the number of groups.
(但し、R’+R”+R3は炭素数2〜4の直鎖または
分岐のアルキレン基、R4,Rs、 R6は炭素数2〜
36の脂肪族、脂環式又は芳香族炭化水素基を表わす、
nは0〜180.mは1〜400である。)である。(However, R'+R"+R3 is a linear or branched alkylene group having 2 to 4 carbon atoms, and R4, Rs, and R6 are straight chain or branched alkylene groups having 2 to 4 carbon atoms.
36 aliphatic, cycloaliphatic or aromatic hydrocarbon groups;
n is 0 to 180. m is 1-400. ).
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の末端変性ポリエーテルアミド樹脂は、ポリエー
テル単位とポリアミド単位とを連結した下記一般式(1
)、 (II)、 (III)又は〔IV〕で示さ
れるポリ(エーテルアミド)単位を主構成単位とする。The terminal-modified polyetheramide resin of the present invention has the following general formula (1) in which polyether units and polyamide units are connected.
), (II), (III) or [IV] as the main structural unit.
ポリ (エーテルアミド)は、例えば末端にアミノ基又
はカルボキシル基を有するポリエーテルと末端にカルボ
キシル基又はアミノ基を有するポリアミドとを縮合反応
にてアミド結合させることにより容易に得ることができ
る。Poly(ether amide) can be easily obtained by, for example, forming an amide bond between a polyether having an amino group or a carboxyl group at the end and a polyamide having a carboxyl group or an amino group at the end through a condensation reaction.
これらCI)〜〔IV〕で示される構成単位は、各々単
独で本発明のポリエーテルアミドを形成するが、場合に
よっては、本発明のポリエーテルアミドはこれらの2種
以上を含む共重合体であってもよい。Each of these structural units represented by CI) to [IV] forms the polyether amide of the present invention by itself, but in some cases, the polyether amide of the present invention may be a copolymer containing two or more of these. There may be.
上記一般式(I)〜(mV)中アルキレン基を表わすR
I 、 Rを及びR3は、エチル基、プロピル基、イソ
プロピル基、テトラメチレン基などの炭素数2〜4の直
鎖又は分岐のアルキレン基であり、その炭素数は2〜4
である。また、整数nはθ〜180、好ましくは0〜6
0程度である。R representing an alkylene group in the above general formulas (I) to (mV)
I, R and R3 are linear or branched alkylene groups having 2 to 4 carbon atoms, such as ethyl group, propyl group, isopropyl group, and tetramethylene group;
It is. In addition, the integer n is θ~180, preferably 0~6
It is about 0.
上記一般式中、R4は炭素数2〜36、好ましくは2〜
25、更に好ましくをよ2〜11の脂肪族、脂環式又は
芳香族炭化水素基であり、後述するポリアミド製造に用
いるラクタム又はアミノカルボン酸の残基である。R5
は炭素数2〜36、好ましくは2〜22、更に好ましく
は2〜7の脂肪族、脂環式又は芳香族炭化水素基であり
、後述するジアミンの残基である。R6は炭素数2〜3
6、好ましくは2〜24、更に好ましくは2〜11の脂
肪族、脂環式又は芳香族炭化水素基であり、後述するジ
カルボン酸の残基である。また、整数mは1〜400、
好ましくは1〜120である。In the above general formula, R4 has 2 to 36 carbon atoms, preferably 2 to 36 carbon atoms.
25, more preferably 2 to 11 aliphatic, alicyclic or aromatic hydrocarbon groups, and are residues of lactams or aminocarboxylic acids used in the production of polyamides, which will be described later. R5
is an aliphatic, alicyclic or aromatic hydrocarbon group having 2 to 36 carbon atoms, preferably 2 to 22 carbon atoms, more preferably 2 to 7 carbon atoms, and is a residue of a diamine described below. R6 has 2 to 3 carbon atoms
6, preferably 2 to 24, more preferably 2 to 11 aliphatic, alicyclic, or aromatic hydrocarbon groups, and is a residue of a dicarboxylic acid described below. In addition, the integer m is 1 to 400,
Preferably it is 1-120.
本発明のポリ (エーテルアミド)を槽底するポリエー
テル単位の含有量は、5〜75重量%、好ましくは10
〜50重量%が、機械的強度及び柔軟性のバランスとい
う点から、好適である。The content of polyether units in the poly(ether amide) of the present invention at the bottom of the tank is 5 to 75% by weight, preferably 10% by weight.
~50% by weight is suitable from the viewpoint of a balance between mechanical strength and flexibility.
本発明の末端変性ポリエーテルアミド樹脂は、ポリ(エ
ーテルアミド)単位からなるポリエーテルアミドの末端
に一定割合の炭化水素基を導入し、末端変性したもので
ある。The terminal-modified polyetheramide resin of the present invention is obtained by introducing a certain proportion of hydrocarbon groups into the terminals of polyetheramide consisting of poly(etheramide) units to modify the terminals.
本発明の末端変性ポリエーテルアミド樹脂が末端に有す
る炭化水素基(末端炭化水素基)としては、炭素数1〜
22のものであり、具体的には、メチル基、エチル、プ
ロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチ
ル基、オクチル基、2−エチルヘキシル基、ノニル基、
デシル基、ウンデシル基、ドデシル基、トリデシル基、
テトラデシル基、テトラデシル基、ペンタデシル基、ヘ
キサデシル基、ヘプタデシル基、オクタデシル基、オク
タデシル基、エイコシル基、トコシル基のような脂肪族
炭化水素基、シクロヘキシル基、メチルシクロヘキシル
基、シクロヘキシルメチル基のような脂環式炭化水素基
、フェニル基、トルイル基、ベンジル基、β−フェニル
エチル基のような芳香族炭化水素基などが挙げられる。The hydrocarbon group (terminal hydrocarbon group) that the terminal-modified polyetheramide resin of the present invention has at the end has 1 to 1 carbon atoms.
22, specifically methyl group, ethyl, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group,
Aliphatic hydrocarbon groups such as tetradecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, octadecyl group, eicosyl group, tocosyl group, alicyclic group such as cyclohexyl group, methylcyclohexyl group, cyclohexylmethyl group Examples include aromatic hydrocarbon groups such as a phenyl group, tolyl group, benzyl group, and β-phenylethyl group.
これらの末端炭化水素基は、ポリエーテルアミドの製造
時に後記するモノカルボン酸および/またはモノア旦ン
を使用することによって導入される。These terminal hydrocarbon groups are introduced by using a monocarboxylic acid and/or a monoamine, which will be described later, during the production of polyether amide.
本発明の変性ポリエーテルアミド樹脂の末端基としては
、上記末端炭化水素基の他に、後述するポリエーテルア
ミド製造の原料に由来するアミノ基および/またはカル
ボキシル基があるが、全末端基の数は、上記末端炭化水
素基、アミノ基および/またはカルボキシル基の数の和
である。本発明においては上記末端炭化水素基の数は全
末端基の数の5〜100%である。この数が少ないと溶
融重合及び溶融成形時の還元性不純物の発生を抑制する
ことができないので5%以上、好ましくは10%以上と
する。また、末端炭化水素基を全末端基数の100%に
近くすることは、製造が容易でなくなるので、工業的に
は好ましくは95%以下、より好ましくは90%以下と
するのがよい。In addition to the above-mentioned terminal hydrocarbon groups, the terminal groups of the modified polyetheramide resin of the present invention include amino groups and/or carboxyl groups derived from the raw materials for producing polyetheramide, which will be described later. is the sum of the numbers of the above terminal hydrocarbon groups, amino groups and/or carboxyl groups. In the present invention, the number of the terminal hydrocarbon groups is 5 to 100% of the total number of terminal groups. If this number is small, the generation of reducing impurities during melt polymerization and melt molding cannot be suppressed, so it is set to 5% or more, preferably 10% or more. Furthermore, if the number of terminal hydrocarbon groups is close to 100% of the total number of terminal groups, production will not be easy, so from an industrial perspective, it is preferably 95% or less, more preferably 90% or less.
本発明のポリエーテルアミド樹脂が末端に有する炭化水
素基の炭素数は、1〜22、好ましくは6〜22、さら
に好ましくは12〜22である。The number of carbon atoms in the terminal hydrocarbon group of the polyetheramide resin of the present invention is 1 to 22, preferably 6 to 22, and more preferably 12 to 22.
該末端炭化水素基としては、上述のような脂肪族炭化水
素基、脂環式炭化水素基、芳香族炭化水素基が挙げられ
るが、そのうち、脂肪族炭化水素基、好ましくは直鎖の
もの、更には炭素数12〜22の長鎖のアルキル基が、
減圧重合時の飛散が少なく分子量制御が容易であるとい
う点で好ましい。Examples of the terminal hydrocarbon group include the above-mentioned aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, among which aliphatic hydrocarbon groups, preferably linear ones, Furthermore, a long chain alkyl group having 12 to 22 carbon atoms,
It is preferable because there is little scattering during vacuum polymerization and molecular weight control is easy.
本発明の末端変性ポリエーテルアミド樹脂は、分子量(
Mn)がio、ooo 〜too、ooo、好ましくは
15.000〜so、oooである。The terminal-modified polyetheramide resin of the present invention has a molecular weight (
Mn) is io, ooo to too, ooo, preferably 15,000 to so, ooo.
分子量は、分析可能な末端基量(アミノ基及びカルボキ
シル基)(μeq/g)と末端変性剤(後述)の使用量
(μeq/ g )との合計を全末端基数とし、次式に
より求めた値である。The molecular weight was determined by the following formula, with the total number of terminal groups being the sum of the amount of terminal groups that can be analyzed (amino groups and carboxyl groups) (μeq/g) and the amount of terminal modifier (described later) (μeq/g) used. It is a value.
次に、本発明の末端変性ポリエーテルアミド樹脂の製造
法について説明する。Next, a method for producing the terminal-modified polyetheramide resin of the present invention will be explained.
ポリ(エーテルアミド)は、例えば末端にアごノ基又は
カルボキシル基を有するポリエーテルと末端にカルボキ
シル基又はアミノ基を有するポリアミドとを縮合反応に
てアミド結合させることにより容易に得ることができる
。Poly(ether amide) can be easily obtained by, for example, forming an amide bond between a polyether having an agono group or a carboxyl group at the end and a polyamide having a carboxyl group or an amino group at the end through a condensation reaction.
末端にアミノ基又はカルボキシル基を有するポリエーテ
ルは、例えば、エチレンオキシド、プロピレンオキシド
、等のアルキレンオキシドやテトラヒドロフランを開環
重合するなどして、ポリエチレンオキシド、ポリプロピ
レンオキシド、ポリテトラメチレンオキシド等のポリエ
ーテルを得、これの末端ヒドロキシル基をアミノ基及び
又はカルボキシル基に置換することにより容易に得られ
る。Polyethers having amino groups or carboxyl groups at the terminals can be prepared by ring-opening polymerization of alkylene oxides such as ethylene oxide, propylene oxide, etc. or tetrahydrofuran. It can be easily obtained by substituting the terminal hydroxyl group with an amino group and/or a carboxyl group.
上記のアミノ基置換の方法としては、ヒドロキシル基の
直接アミノ化またはシアノエチル化した後、還元アミノ
化する方法が挙げられ、カルボキシル基置換の方法とし
ては、酸化カルボニル化による方法が挙げられる。Examples of the above-mentioned amino group substitution method include direct amination of the hydroxyl group or cyanoethylation followed by reductive amination, and carboxyl group substitution includes oxidative carbonylation.
本発明においては、原料ポリエーテルとしては、両末端
にアミノ基を有するポリエーテル(5)又は両末端にカ
ルボキシル基を有するポリエーテル(′b)が好適に使
用される。In the present invention, polyether (5) having amino groups at both ends or polyether ('b) having carboxyl groups at both ends is preferably used as the raw material polyether.
HlN−R’0→R” 0 )−R’ −N H、(a
lHOOC=R’0→R”0h−R’−COO)I
伽)(R’、R”、R3は前記に同し)
一方、末端にカルボキシル基およびアミノ基を有するポ
リアミドは、3ji環以上のラクタムの開環重合、重合
可能なアミノカルボン酸の重縮合またはジカルボン酸と
ジアミンの重縮合によって直接得ることができる。HlN-R'0→R''0)-R'-NH, (a
lHOOC=R'0→R"0h-R'-COO)I
(R', R", R3 are the same as above) On the other hand, polyamides having carboxyl groups and amino groups at the terminals can be produced by ring-opening polymerization of lactams having 3 or more rings, polycondensation of polymerizable aminocarboxylic acids, or It can be obtained directly by polycondensation of dicarboxylic acids and diamines.
ラクタムとしては、具体的には、ε−カプロラクタム、
エナントラクタム、カプリルラクタム、ラウリルラクタ
ム、α−ピロリドン、α−ピペリドン等が挙げられる。Specifically, the lactam includes ε-caprolactam,
Examples include enantholactam, capryllactam, lauryllactam, α-pyrrolidone, α-piperidone, and the like.
重合可能なアミノカルボン酸としては、好ましくはω−
ア旦ノ酸が挙げられ、通常、炭素数2〜25のω−アご
ノ酸が使用される。具体的には、6−アミノカプロン酸
、7−アミノへブタン酸、9−アミノノナン酸、11−
アミノウンデカン酸等が挙げられる。The polymerizable aminocarboxylic acid is preferably ω-
Amanoic acid is mentioned, and ω-ahanoic acid having 2 to 25 carbon atoms is usually used. Specifically, 6-aminocaproic acid, 7-aminohebutanoic acid, 9-aminononanoic acid, 11-
Examples include aminoundecanoic acid.
ジカルボンとしては、通常、炭素数2〜36のジカルボ
ン酸が使用され、具体的には、マロン酸、コハク酸、グ
ルタル酸、アジピン酸、ピメリン酸、スペリン酸、アゼ
ライン酸、セバシン酸、ウンデカンジオン酸、ドデカン
ジオン酸、トリデカジオン酸、テトラデカジオン酸、ヘ
キサデカジオン酸、ヘキサデセンジオン酸、オクタデカ
ジオン酸、オクタデセンジオン酸、エイコサンジオン酸
、エイコセンジオン酸、エイコサジエンジオン酸、トコ
サンジオン酸、2.2.4−)リメチルアジピン酸のよ
うな脂肪族ジカルボン酸、1.4−シクロヘキサンジカ
ルボン酸のような脂環式ジカルボン酸、テレフタル酸、
イソフタル酸、フタル酸、キシリレンジカルボン酸のよ
うな芳香族ジカルボン酸等が挙げられる。As the dicarboxylic acid, a dicarboxylic acid having 2 to 36 carbon atoms is usually used, and specific examples include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, and undecanedioic acid. , dodecanedioic acid, tridecadionic acid, tetradecadionic acid, hexadecadionic acid, hexadecenedioic acid, octadecadionic acid, octadecenedioic acid, eicosandioic acid, eicocenedioic acid, eicosadienedionic acid, tocosandioic acid , 2.2.4-) aliphatic dicarboxylic acids such as limethyladipic acid, cycloaliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, terephthalic acid,
Examples include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid, and xylylene dicarboxylic acid.
また炭素数36のジカルボン酸として二量体化脂肪酸が
挙げられる。二量体化脂肪酸は、脂肪酸、例えば炭素数
8〜24の飽和、エチレン系不飽和、アセチレン系不飽
和、天然または合成−塩基性脂肪酸を重合して得た重合
脂肪酸である。Furthermore, examples of dicarboxylic acids having 36 carbon atoms include dimerized fatty acids. Dimerized fatty acids are polymerized fatty acids obtained by polymerizing fatty acids, such as saturated, ethylenically unsaturated, acetylenically unsaturated, natural or synthetic basic fatty acids having 8 to 24 carbon atoms.
また、ジアミンとしては、通常、炭素数2〜24のジア
ミンが使用され、具体的には、エチレンジアミン、トリ
メチレンジアミン、テトラメチレンジアミン、ペンタメ
チレンシアごン、ヘキサメチレンジアミン、ヘプタメチ
レンジアミン、オクタメチレンシアくン、ノナメチレン
ジアミン、デカメチレンジアミン、ウンデカメチレンジ
アミン、ドデカメチレンジアミン、トリデカメチレンジ
アミン、ヘキサデカメチレンシア旦ン、オクタデカメチ
レンジアミン、2,2.4 (または2,4゜4)−ト
リメチルへキサメチレンジアミンのような脂肪族ジアミ
ン、シクロヘキサンジアミン、メチルシクロヘキサンシ
アごン、ビス−(4,4’−ア逅ノシクロへキシル)メ
タンのような脂環式ジアミン、キシリレンジアミンのよ
うな芳香族ジアミン等が挙げられる。炭素数36のジア
ミンとして二量体化脂肪酸のカルボキシル基をアミノ基
に変換した二量体アミンが挙げられる。In addition, as the diamine, diamines having 2 to 24 carbon atoms are usually used, and specifically, ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, etc. Cia-kun, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, hexadecamethylene diamine, octadecamethylene diamine, 2,2.4 (or 2,4゜4 )-Trimethylhexamethylene diamine, aliphatic diamines such as cyclohexane diamine, methylcyclohexane diamine, bis-(4,4'-anocyclohexyl)methane, and xylylene diamine. Examples include aromatic diamines such as Examples of diamines having 36 carbon atoms include dimeric amines obtained by converting the carboxyl groups of dimerized fatty acids into amino groups.
以上のようなポリアミドの具体例としては、例えば、ナ
イロン4. 6. 7. 8. 11. 12.6゜6
.6.9.6.10,6.11.6.12,6T、6/
66.6/12.6/6T等が挙げられる。Specific examples of the polyamides mentioned above include nylon 4. 6. 7. 8. 11. 12.6°6
.. 6.9.6.10, 6.11.6.12, 6T, 6/
Examples include 66.6/12.6/6T.
上記ポリアミドのうちで、ラクタムの開環重縮合または
ω−アミノ酸の重縮合によるものについては、下記−数
式(C)又は(blで表わされるポリアミドが好適に使
用される。Among the above-mentioned polyamides, polyamides represented by the following formula (C) or (bl) are preferably used for polyamides produced by ring-opening polycondensation of lactams or polycondensation of ω-amino acids.
H−(−N)IR’c)=−NHR”N)It
(d)(R’、R’、R−は前記に同じ〉
上記−数式(C)で示される両末端カルボキシル基のポ
リアミドは、ラクタムの開環重縮合による基本ポリアミ
ドに前述のジカルボン酸を付加させることにより得られ
、また、上記−数式1d)で示される両末端アごノ基の
ポリアミドは、同基本ポリアミドに前述のジアミンを付
加させることにより得られる。H-(-N)IR'c)=-NHR"N)It
(d) (R', R', R- are the same as above) The polyamide with carboxyl groups at both ends represented by formula (C) above is obtained by adding the above-mentioned dicarboxylic acid to the basic polyamide obtained by ring-opening polycondensation of lactam. The polyamide having agono groups at both ends represented by the above-mentioned formula 1d) can be obtained by adding the above-mentioned diamine to the same basic polyamide.
一方、ジカルボン酸とジアミンの重縮合によるポリアミ
ドは、いずれかの原料を理論量以上使用することにより
、直接、下記の両末端カルボキシル基のポリアミド(e
l又は両末端アミノ基のポリアミド(f)を得ることが
できる。On the other hand, polyamides produced by polycondensation of dicarboxylic acids and diamines can be produced directly by using more than the theoretical amount of either raw material.
A polyamide (f) having one or both terminal amino groups can be obtained.
以上のように、本発明のポリ (エーテルアミド)は、
前述のような末端にアミノ基又はカルボキシル基を有す
るポリエーテルと末端にカルボキシル基又はアミノ基を
有するボリア果ドとを縮合させて得られる上記−数式(
1)、(■)、 (III)又は〔IV〕で示される
構成単位からなるものである。As described above, the poly(ether amide) of the present invention is
The above-mentioned formula (
1), (■), (III) or [IV].
即ち、上記−数式(1)又は(If)は、前述の一般式
(a)で示される両末端アミノ基のポリエーテルと一般
式(C1又は(e)で示される両末端カルボキシル基の
ポリアミドとを縮合させて得られる繰り返し構造単位で
あり、−数式(II)又は〔IV〕は、前述の一般式(
b)で示される両末端カルボキシル基のポリエーテルと
一般式(d)又は(f)で示される両末端アミノ基のポ
リアミドとを縮合させて得られる繰り返し構造単位であ
る。That is, the above formula (1) or (If) is a polyether having amino groups at both ends represented by the general formula (a) and a polyamide having carboxyl groups at both ends represented by the general formula (C1 or (e)). - Formula (II) or [IV] is a repeating structural unit obtained by condensing the above-mentioned general formula (
It is a repeating structural unit obtained by condensing a polyether having carboxyl groups at both ends represented by b) and a polyamide having amino groups at both ends represented by general formula (d) or (f).
本発明の末端変性ポリエーテルアミド樹脂は、このよう
なポリ (エーテルアミド)の末端に炭化水素基を導入
し、末端変性したものである。The terminal-modified polyetheramide resin of the present invention is obtained by introducing a hydrocarbon group into the terminal of such poly(etheramide) to modify the terminal.
本発明の末端変性ポリエーテルアミド樹脂は、前述のよ
うなポリ (エーテルアミド)の末端に、一定割合以上
の炭化水素基を導入し、末端変性したものである。The terminal-modified polyetheramide resin of the present invention is obtained by introducing a certain proportion or more of hydrocarbon groups into the terminals of the poly(etheramide) described above to modify the terminals.
ポリ(エーテルアミド〉の末端変性は、ポリ(エーテル
アミド)の末端基であるアミノ基及びカルボキシル基に
、末端変性剤としてモノカルボン酸及び/又はモノアミ
ンを反応させることにより行われる。Terminal modification of poly(ether amide) is carried out by reacting the amino group and carboxyl group, which are the terminal groups of poly(ether amide), with a monocarboxylic acid and/or a monoamine as a terminal modifier.
モノカルボン酸としては、通常、炭素数2〜23程度の
モノカルボン酸が使用され、具体的には、酢酸、プロピ
オン酸、醋酸、吉草酸、カプロン酸、エナント酸、カプ
リル酸、ペラルゴン酸、カプリン酸、ウンデカン酸、ラ
ウリル酸、トリデカン酸、ミリスチン酸、ペンタデカン
酸、パルミチン酸、ステアリン酸、アラキン酸、ベヘン
酸、ξリストレイン酸、オレイン酸、リノール酸のよう
な脂肪族モノカルボン酸、シクロヘキサンカルボン酸、
メチルシクロヘキサンカルボン酸のような脂環式モノカ
ルボン酸、安息香酸、トルイル酸、エチル安息香酸、フ
ェニル酢酸のような芳香族モノカルボン酸等が挙げられ
る。なお、反応中、上記酸と同じ役割を果し得る相当す
る誘導体、例えば酸無水物、エステル、アミドなども使
用することができる。As the monocarboxylic acid, a monocarboxylic acid having about 2 to 23 carbon atoms is usually used, and specific examples include acetic acid, propionic acid, acetic acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, and capric acid. acids, aliphatic monocarboxylic acids such as undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, ξ ristoleic acid, oleic acid, linoleic acid, cyclohexanecarboxylic acid acid,
Examples include alicyclic monocarboxylic acids such as methylcyclohexanecarboxylic acid, and aromatic monocarboxylic acids such as benzoic acid, toluic acid, ethylbenzoic acid, and phenylacetic acid. Note that corresponding derivatives, such as acid anhydrides, esters, amides, etc., which can play the same role as the above-mentioned acids during the reaction can also be used.
一方、モノアごンとしては、通常、炭素数1〜22程度
の各種モノアミンが使用され、具体的には、メチルアミ
ン、エチルアミン、プロピルア果ン、ブチルア箋ン、ペ
ンチルアミン、ヘキシルアミン、ヘプチルアミン、オク
チルアミン、2−エチルヘキシルアミン、ノニルアミン
、デシルアミン、ウンデシルアミン、ドデシルアミン、
トリデシルアミン、テトラデシルアミン、ペンタデシル
アミン、ヘキサデシルアミン、ヘプタデシルアミン、オ
クタデジルア逅ン、エイコシルアミン、トコシルアミン
、オクタデシレンアξンのような脂肪族モノアミン、シ
クロヘキシルアミン、メチルシクロヘキシルアミンのよ
うな脂環式モノアミン、ベンジルアミン、β−フェニル
エチルアξンのような芳香族モノアミン等が挙げられる
。On the other hand, as monoagons, various monoamines having about 1 to 22 carbon atoms are usually used, and specifically, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, Octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine,
Aliphatic monoamines such as tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, eicosylamine, tocosylamine, octadecylamine, fats such as cyclohexylamine, methylcyclohexylamine Examples include cyclic monoamines, benzylamine, and aromatic monoamines such as β-phenylethyl ξ.
上記反応により、ポリ(エーテルアミド)の末端アミノ
基及び/又はカルボキシル基には炭化水素基導入剤とし
て使用したモノカルボン酸及び/又はモノアミンに対応
する炭化水素基が導入される。Through the above reaction, a hydrocarbon group corresponding to the monocarboxylic acid and/or monoamine used as the hydrocarbon group-introducing agent is introduced into the terminal amino group and/or carboxyl group of the poly(ether amide).
本発明の末端変性ポリエーテルアミド樹脂の製造は、公
知の縮合反応により行うことができる。The terminal-modified polyetheramide resin of the present invention can be produced by a known condensation reaction.
先ず、ポリアミド原料から目的とするポリアミドを得、
次いで、これに、末端基を適宜変性した前述のポリエー
テル添加して縮合反応を行う、末端変性に使用されるモ
ノカルボン酸及び/又はモノアミンは、上記縮合反応開
始時から減圧下の反応を始めるまでの任意の段階で添加
することができる。また、モノカルボン酸とモノアミン
とを併用するときは同時に加えても、別々に加えてもよ
い。First, obtain the desired polyamide from the polyamide raw material,
Next, the above-mentioned polyether whose terminal groups have been appropriately modified is added to this to perform a condensation reaction.The monocarboxylic acid and/or monoamine used for terminal modification starts the reaction under reduced pressure from the start of the above-mentioned condensation reaction. It can be added at any stage up to. Furthermore, when a monocarboxylic acid and a monoamine are used together, they may be added at the same time or separately.
本発明の末端変性ポリエーテルアミド樹脂は、食品関連
分野、主に食品に直接接触を必要とする包装体、具体的
にはフィルム、シート、ブロー容器等として用いること
ができる。The terminal-modified polyetheramide resin of the present invention can be used in food-related fields, mainly as packaging bodies that require direct contact with foods, specifically films, sheets, blow containers, etc.
また本発明で言う包装体とはフィルム、シート、ブロー
容器等を含む包装材料のことであり、Tダイ法、インフ
レーション法等の押出成形の他射出成形、ブロー成形、
真空成形などの一般に熱可塑性樹脂で公知の成形方法に
供することにより成形される。また、成形性や物性を損
わない限りにおいて他の成分、例えば顔料、染料、耐熱
剤、酸化防止剤、耐候剤、滑剤、結晶核剤、滞電防止剤
、可塑剤、他の重合体等の添加導入することができる。In addition, the packaging body referred to in the present invention refers to packaging materials including films, sheets, blow containers, etc. In addition to extrusion molding such as T-die method and inflation method, injection molding, blow molding,
It is molded by subjecting it to a generally known molding method for thermoplastic resins, such as vacuum molding. In addition, other ingredients such as pigments, dyes, heat resistant agents, antioxidants, weathering agents, lubricants, crystal nucleating agents, antistatic agents, plasticizers, other polymers, etc. may be added as long as they do not impair moldability or physical properties. can be added.
また本発明の末端変性ポリエーテルアミド樹脂からなる
包装体がフィルムまたはシートである場合は未延伸のま
ま使用しても、公知の方法で延伸して使用してもよい。Further, when the package made of the terminal-modified polyetheramide resin of the present invention is a film or sheet, it may be used unstretched or after being stretched by a known method.
また、該包装体に対し共押出法、ラミネート法等の公知
の方法で公知の樹脂を積層して使用してもよい。Further, a known resin may be laminated onto the package by a known method such as a coextrusion method or a lamination method.
以下本発明について実施例により更に詳しく説明するが
、本発明はこれら実施例に限定されるものではない。EXAMPLES The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to these Examples.
なお、実施例においては、各種測定値は以下の方法によ
り求めたものである。In addition, in the examples, various measured values were obtained by the following methods.
+1) 末端基分析
炭化水素基の数は、変性ポリエーテルアミド樹脂を塩酸
を用いて加水分解後、ガスクロマトグラフィーにより測
定した。アミノ基は、ポリアミドをフェノールに溶解し
、0.05 N塩酸で滴定して測定した。また、カルボ
キシル基は、ポリアミドをベンジルアルコールに溶解し
、0.IN苛性ソーダで滴定して測定した。+1) End group analysis The number of hydrocarbon groups was measured by gas chromatography after hydrolyzing the modified polyetheramide resin using hydrochloric acid. Amino groups were measured by dissolving polyamide in phenol and titrating with 0.05 N hydrochloric acid. In addition, carboxyl groups can be obtained by dissolving polyamide in benzyl alcohol. Measured by titration with IN caustic soda.
(2) 相対粘度;ウベローデ粘度管を用い、m−ク
レゾール中1%濃度で求めたく30℃〉。(2) Relative viscosity; determined at 1% concentration in m-cresol using an Ubbelohde viscosity tube at 30°C>.
(3) 末端変性率
(4) 低分子化合物量測定
ベレット10gを脱塩水100gで121℃×20分間
抽出し、常温迄冷却した後、0.2μmのテフロンフィ
ルターを通液させ、濾液を乾固後、重量を測定した。(3) Terminal modification rate (4) Measurement of low molecular weight compound amount 10 g of the pellet was extracted with 100 g of demineralized water at 121°C for 20 minutes. After cooling to room temperature, the liquid was passed through a 0.2 μm Teflon filter, and the filtrate was evaporated to dryness. After that, the weight was measured.
(5) 臭気物質測定
セプタム付ガラス管にサンプル10gを入れ、N、置換
後100℃×30分加熱しヘッドスペースに滞留するガ
ス0.5wjをガスタイトシリンダーでサンプリングし
GC分析した。(5) Measurement of Odorous Substances 10 g of a sample was placed in a glass tube with a septum, replaced with N, heated at 100° C. for 30 minutes, and 0.5 wj of gas remaining in the head space was sampled with a gastight cylinder and analyzed by GC.
実施例1〜6
2001のオートクレーブに、表1記載のポリアミド原
料を仕込み、N2雰囲気にして密閉し、圧カ一定(IO
KG)で240℃に昇温し撹拌下2時間加圧下に反応を
行った後、表1記載のポリエーテル及び末端変性剤を添
加し、さらに撹拌下2時間加圧反応を行った。徐々に放
圧して所定の圧力迄減圧し、2時間減圧下反応を行った
。Examples 1 to 6 A 2001 autoclave was charged with the polyamide raw materials listed in Table 1, sealed in an N2 atmosphere, and maintained at a constant pressure (IO
After heating the mixture to 240° C. with stirring and carrying out a reaction under pressure for 2 hours, the polyether and terminal modifier listed in Table 1 were added, and the reaction was further carried out under pressure for 2 hours with stirring. The pressure was gradually released to a predetermined pressure, and the reaction was carried out under reduced pressure for 2 hours.
撹拌を留め、N8を導入して常圧に復圧後、ストランド
として抜き出してペレット化した。The stirring was stopped, N8 was introduced to restore the pressure to normal pressure, and the mixture was extracted as a strand and pelletized.
このようにして得られたベレットを100℃熱水抽出(
水比3.0.50分XIO回回分抽出)及び乾燥後、3
.6オンス射出成形機(東芝機械■製)を用いて樹脂温
度240℃、金型温度60℃にて試験片を成形し、酸形
前後で易抽出低分子化合物及び臭気測定を行った。結果
を表1に示した。The pellets thus obtained were extracted with hot water at 100°C (
water ratio 3.0.50 min XIO batch extraction) and after drying, 3
.. A test piece was molded using a 6-ounce injection molding machine (manufactured by Toshiba Machine ■) at a resin temperature of 240°C and a mold temperature of 60°C, and easily extractable low molecular weight compounds and odor were measured before and after the acid form. The results are shown in Table 1.
比較例1.2
末端変性剤を加えない以外は実施例1〜6と同様の操作
を行った。結果を表1に示した。Comparative Example 1.2 The same operations as Examples 1 to 6 were performed except that no terminal modifier was added. The results are shown in Table 1.
本願発明の末端変性ポリエーテルア累ド樹脂は、溶融重
合時や成形時の低分子臭気物質や低分子化合物の発生が
大巾に抑制され、熱室、特に食品包装用にフィルムや容
器等に好適である。The terminal-modified polyether composite resin of the present invention greatly suppresses the generation of low-molecular-weight odorous substances and low-molecular compounds during melt polymerization and molding, and is suitable for heat chambers, especially films and containers for food packaging. be.
Claims (1)
で示される構成単位からなり、末端に炭素数1〜22の
炭化水素基を有する分子量10,000〜100,00
0ポリエーテルアミドであり、該炭化水素基の数が該ポ
リエーテルアミドの全末端基の数の5〜100%である
末端変性ポリエーテルアミド樹脂。 ▲数式、化学式、表等があります▼ ・・・〔 I 〕 ▲数式、化学式、表等があります▼ ・・・〔II〕 ▲数式、化学式、表等があります▼ ・・・〔III〕 ▲数式、化学式、表等があります▼ ・・・〔IV〕 (但し、R^1、R^2、R^3は炭素数2〜4の直鎖
または分岐のアルキレン基、R^4、R^5、R^6は
炭素数2〜36の脂肪族、脂環式又は芳香族炭化水素基
を表わす。nは0〜180、mは1〜400である。)(1) The following structural formula [I], [II], [III] or [IV]
Consisting of the structural unit represented by, and having a hydrocarbon group having 1 to 22 carbon atoms at the end and a molecular weight of 10,000 to 100,00
1. A terminal-modified polyetheramide resin in which the number of hydrocarbon groups is 5 to 100% of the total number of terminal groups of the polyetheramide. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・[II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・[III] ▲Mathematical formulas , chemical formulas, tables, etc. ▼ ... [IV] (However, R^1, R^2, R^3 are linear or branched alkylene groups having 2 to 4 carbon atoms, R^4, R^5 , R^6 represents an aliphatic, alicyclic or aromatic hydrocarbon group having 2 to 36 carbon atoms. n is 0 to 180, and m is 1 to 400.)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3473390A JP2881908B2 (en) | 1990-02-15 | 1990-02-15 | Terminally modified polyether amide resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3473390A JP2881908B2 (en) | 1990-02-15 | 1990-02-15 | Terminally modified polyether amide resin |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH03237131A true JPH03237131A (en) | 1991-10-23 |
JP2881908B2 JP2881908B2 (en) | 1999-04-12 |
Family
ID=12422520
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3473390A Expired - Fee Related JP2881908B2 (en) | 1990-02-15 | 1990-02-15 | Terminally modified polyether amide resin |
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JP (1) | JP2881908B2 (en) |
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JP2006520835A (en) * | 2003-03-20 | 2006-09-14 | アリゾナ・ケミカル・カンパニー | Polyamide-polyether block copolymer |
WO2013105607A1 (en) * | 2012-01-12 | 2013-07-18 | 三菱瓦斯化学株式会社 | Polyether polyamide elastomer |
WO2014027647A1 (en) * | 2012-08-14 | 2014-02-20 | 三菱瓦斯化学株式会社 | Moisture-absorbing/releasing material |
WO2014168060A1 (en) * | 2013-04-09 | 2014-10-16 | 三菱瓦斯化学株式会社 | Metal-coating material |
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JP2017061672A (en) * | 2015-06-26 | 2017-03-30 | アルケマ フランス | Peba for direct adhesion to tpe |
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1990
- 1990-02-15 JP JP3473390A patent/JP2881908B2/en not_active Expired - Fee Related
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Publication number | Priority date | Publication date | Assignee | Title |
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US8114424B2 (en) | 2003-03-20 | 2012-02-14 | Arizona Chemical Company, Llc | Polyamide-polyether block copolymer |
US8114387B2 (en) | 2003-03-20 | 2012-02-14 | Arizona Chemical Company, Llc | Polyamide-polyether block copolymer |
US8119741B2 (en) | 2003-03-20 | 2012-02-21 | Arizona Chemical Company, Llc | Polyamide-polyether block copolymer |
US8119149B2 (en) | 2003-03-20 | 2012-02-21 | Arizona Chemical Company, Llc | Polyamide-polyether block copolymer |
JP2006520835A (en) * | 2003-03-20 | 2006-09-14 | アリゾナ・ケミカル・カンパニー | Polyamide-polyether block copolymer |
CN104024305A (en) * | 2012-01-12 | 2014-09-03 | 三菱瓦斯化学株式会社 | Polyether Polyamide Elastomer |
WO2013105607A1 (en) * | 2012-01-12 | 2013-07-18 | 三菱瓦斯化学株式会社 | Polyether polyamide elastomer |
JPWO2013105607A1 (en) * | 2012-01-12 | 2015-05-11 | 三菱瓦斯化学株式会社 | Polyether polyamide elastomer |
WO2014027647A1 (en) * | 2012-08-14 | 2014-02-20 | 三菱瓦斯化学株式会社 | Moisture-absorbing/releasing material |
JP2014037471A (en) * | 2012-08-14 | 2014-02-27 | Mitsubishi Gas Chemical Co Inc | Moisture absorbing and discharging material |
US9512314B2 (en) | 2012-08-14 | 2016-12-06 | Mitsubishi Gas Chemical Company, Inc. | Polyether polyamide composition |
WO2014168060A1 (en) * | 2013-04-09 | 2014-10-16 | 三菱瓦斯化学株式会社 | Metal-coating material |
CN105121510A (en) * | 2013-04-09 | 2015-12-02 | 三菱瓦斯化学株式会社 | Metal-coating material |
JP2017061672A (en) * | 2015-06-26 | 2017-03-30 | アルケマ フランス | Peba for direct adhesion to tpe |
Also Published As
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